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    • 专利摘要:
    CATALYST FOR TREATING EXHAUST GAS CATALYST ARTICLE FOR TREATING EXHAUST GAS AND METHOD FOR TREATING EXHAUST GAS. An exhaust gas treatment catalyst is provided, particularly for the selective reduction of NOx, and methods for using it, in which the catalyst includes a mixture of a transition metal-promoted zeolite and an un-promoted zeolite, in which both zeolites have the same type of main chain, which is selected from CHA, AEI, AFX, LEV and SFW.
    公开号:BR112016004021B1
    申请号:R112016004021-0
    申请日:2014-08-29
    公开日:2021-01-12
    发明作者:Guy Richard Chandler；Alexander Nicholas Michael Green；Paul Richard Phillips
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    Field of the Invention:
    [001] The present invention relates to catalysts, articles, and methods for treating combustion exhaust gas. Description of Related Art:
    [002] The combustion of hydrocarbon fuel produces exhaust gas that largely contains relatively benign nitrogen (N2), water vapor (H2O), and carbon dioxide (CO2). But the exhaust gas also contains, in a relatively small part, harmful and / or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from unburned fuel, nitrogen oxides (NOx) ) from excessive combustion temperatures, and particulate material (mostly soot). To mitigate the environmental impact of exhaust gas released into the atmosphere, it is desirable to eliminate or reduce the amount of undesirable components, preferably by a process that, in turn, does not generate other harmful or toxic substances.
    [003] NOx, which includes nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O), is a costly component to remove from the exhaust gas generated by poorly combustion engines (eg engines diesel and gas turbines). The reduction from NOx to N2 is particularly problematic in the low-burning exhaust gas since the exhaust gas contains enough oxygen to favor oxidative reactions instead of reduction. However, NOx can be reduced by a process commonly known as Selective Catalytic Reduction (SCR).
    [004] An SCR process involves the conversion of NOx, in the presence of a catalyst and with the aid of a nitrogen reducing agent, such as ammonia, in elementary nitrogen (N2) and water. In an SCR process, ammonia is added to an exhaust gas stream before contacting the exhaust gas with the SCR catalyst. The reducer is absorbed into the catalyst and the NOx reduction reaction occurs as the gases pass through or over the catalyzed substrate. Chemical routes for stoichiometric SCR reactions using ammonia include: 2NO + 4NH3 + 2O2 ^ 3N2 + 6H2O 2NO2 + 4NH3 + O2 ^ 3N2 + 6H2O
    [005] N2O is produced in limited quantities by combustion. However, undesirable processes that occur in SCR systems also include several competitive non-selective reactions with oxygen, which is abundant in the system. These reactions can both produce secondary emissions including the production of N2O. Commercial SCR catalysts, including vanadium, iron zeolites, and copper zeolites, all produce N2O. Exhaust gas treatment systems, particularly where the NO2 content has increased to exceed the NO level in the feed gas, allow the formation of N2O through routes such as: 8 NO2 + 6 NH3 ^ 7 N2O + 9 H2O 4 NO2 + 4 NH3 + O2 ^ 4 N2O + 6 H2O 2 NH3 + 2 O2 ^ N2O + 3 H2O
    [006] Appropriately, there is still a need for improved SCR catalysts that provide improved NOx conversion and reduced N2O composition. The present invention satisfies these needs, among others. SUMMARY OF THE INVENTION
    [007] In general, zeolite synthesis produces zeolites in the form of H + or alkaline. These forms of zeolite alone have catalytic properties, but their SCR performance is typically enhanced by subjecting them to a cation exchange in which a portion of ionic species existing on the surface and / or within the pores of the structure is replaced by cations of transition metal, such as Cu2 +. The SCR performance of zeolite, therefore, can be promoted by loosely retaining one or more transition metal ions to the molecular sieve structure. Surprisingly, it has been found that certain catalyst mixtures containing both a metal-promoted zeolite and an un-promoted zeolite of the same structure have SCR performance compared to any of these components used separately. The synergistic effect of such mixtures is both unexpected and unpredictable. And this surprising synergistic effect occurs over a wide temperature range.
    [008] Appropriately, in one aspect of the invention, a catalyst composition is provided to treat an exhaust gas comprising a mixture of (a) a first transition metal exchange zeolite having a first structure selected from CHA , AEI, AFX, LEV, and SFW, and (b) a second zeolite having a second structure selected from CHA, AEI, AFX, LEV, and SFW, where the first and second types of structure are the same, and the second zeolite is primarily in at least one of H + form, NH4 + form, alkaline form, or alkaline earth form.
    [009] According to another aspect of the invention, a method is provided for treating an exhaust gas comprising the step of contacting an exhaust gas stream containing NOx and a reducer with a catalyst mixture described herein; where the step of contacting selectively converts at least a portion of NOx to N2 and water.
    [0010] In accordance with another aspect of the invention, a method is provided for treating exhaust gas comprising the step of contacting an ammonia-containing emission gas with a catalyst article containing an oxidation catalyst and an SCR catalyst mixture described herein ; wherein the contacting step (a) oxidizes at least a portion of the ammonia to form N2, H2O, and optionally secondary NOx; and (b) selectively reduces secondary NOx to N2 and H2O.
    [0011] According to another aspect of the invention, a catalytic article is provided comprising a catalyst composition described herein and a substrate on which and / or on which the catalyst is arranged.
    [0012] According to a further aspect of the invention, a system is provided for treating exhaust gas comprising (a) a catalyst article described herein; and (b) one or more upstream components selected from a diesel oxidation catalyst, a NOx absorption catalyst, a poor NOx trap, a diesel particulate filter, an NH3 injector, and a SCR; and (c) optionally an ammonia leak catalyst downstream and / or a diesel particulate filter. BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows comparative NOx conversion performance at 200 ° C of certain embodiments of the present invention; Figure 2 shows comparative NOx conversion performance at 500 ° C of certain embodiments of the present invention; and Figure 3 shows NOx conversion performance at 600 ° C of an embodiment of the present invention compared to a conventional SCR catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
    [0013] In a preferred embodiment, the invention is directed to a catalyst article to improve ambient air quality, particularly to improve purge or other exhaust gas emissions generated by low combustion internal combustion engines, power plants, gas turbines, and the like. Exhaust gas emissions are improved, at least in part, by reducing the concentrations of NOx and / or NH3 of poorly burned exhaust gas over a wide operating temperature range. Useful catalysts are those that selectively reduce NOx and / or reduce ammonia leakage in an oxidizing environment (ie, an SCR catalyst and / or ASC catalyst).
    [0014] In certain embodiments, the catalyst is a mixture of a zeolite promoted by metal and an un-promoted zeolite having the same structure. As used here, the thermal mixture means a uniform heterogeneous mixture of two or more materials, both of which can be used alone for the same purpose as the mixture. Preferably, the ratio of the non-promoted zeolite to the metal-promoted zeolite is about 0.1 to about 1, such as about 0.1 about 0.5, about 0.3 to about 0.5, about from 0.5 to about 0.75, and from 0.5 to about 1.
    [0015] As used here, the term “promoted by metal” in relation to a zeolite means a zeolite having a transition metal exchange solution. As a corollary, “non-promoted” zeolites are those that are free of transition metal exchange solution, for example, zeolites in a form of H +, NH4 +, alkali metal, or alkaline earth metal. Non-promoted zeolites include those that are synthesized in H + or alkali metal form and also synthesized zeolites that have undergone ion exchange, either completely or partially, to produce forms of NH4 + or alkaline earth metal.
    [0016] The metal-promoted zeolite component of the catalyst mixture is preferably promoted with a transition metal. The transition metal can be any of the recognized catalytically active metals that are used in the catalyst industry to form metal exchange zeolites, particularly those metals that are known to be catalytically active to selectively reduce NOx in an exhaust gas derived from a poor burning combustion process. Transition metals useful in the present invention include manganese, iron, cobalt, nickel, and copper. A particularly preferred transition metal is copper. In certain embodiments, the catalyst mixture is free or substantially free of any transition metals other than copper. The term "substantially free" with respect to the presence of a transition metal, means that the catalyst does not contain the transition metal or contains only a minimal amount of metal. If the metal is present, its concentration is low enough so as not to affect the basic functionality of the catalyst. For example, a catalyst mixture substantially free of a transition metal contains less than 0.1, less than 0.01, or less than 0.001 weight percent of metal.
    [0017] In certain embodiments, the promoter metal is present in a zeolite material in a concentration of about 0.1 to about 10 weight percent (% by weight) based on the total weight of the zeolite, for example from from about 0.5% by weight to about 5% by weight, from about 0.5 to about 1% by weight, from about 1 to about 5% by weight, about 2 , 5% by weight to about 3.5% by weight, and about 3% by weight to about 3.5% by weight. For embodiments using copper the concentration of these transition metals in a zeolite material is preferably about 1 to about 5 weight percent, more preferably about 2.5 to about 3.5 weight percent.
    [0018] In one embodiment, the metal-promoted zeolite component is a metal-exchange zeolite created by mixing the zeolite in a solution containing soluble precursors of the transition promoting metal. The pH of the solution can be adjusted to induce precipitation of catalytically active metal cations into or within the zeolite structure (but not including the zeolite structure). For example, in a preferred embodiment, a zeolite material is immersed in a solution containing copper nitrate for a time sufficient to allow the incorporation of catalytically active copper cations into the molecular sieve structure by ion exchange. Unchanged copper ions are precipitated. Depending on the application, a portion of the unchanged ions may remain in the molecular sieve material as free copper. the metal exchange zeolite can then be washed, dried, and calcined.
    [0019] In general, ion exchange of the catalytic metal cation in a zeolite pore or on a zeolite surface can be performed at room temperature or at a temperature up to about 80 ° C for a period of about 1 to 24 hours at a pH of about 7. The resulting metal-promoted zeolite material is preferably dried at about 100 to 120 ° C overnight and calcined at a temperature of at least about 500 ° C.
    [0020] The term “zeolite”, as used here, means an aluminosilicate molecular sieve having a unique structure, such as that recognized by the International Zeolite Association (IZA) Structure Commission. Preferred zeolites are synthetic zeolites. Zeolites useful in the present invention preferably have a silica to alumina (SAR) ratio of about 10 to about 40, such as about 10 to about 15, about 15 to about 35, or about 20 to about 25. Thus, for the present invention, zeolites can be distinguished from other types of molecular sieves, such as silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), and ferrosilicates.
    [0021] The ratio of silica to alumina of a zeolite can be determined by conventional analysis. This ratio should represent, as close as possible, the ratio in the structure crystal of the rigid atomic zeolite and to exclude silicon or aluminum in the binder or in the cationic form or otherwise within the channels. Since it can be difficult to directly measure the ratio of zeolite silica to alumina after being combined with a binder material, particularly an alumina binder, these silica to alumina ratios are expressed in terms of zeolite SAR alone, that is, before combining the zeolite with the other catalyst components.
    [0022] In certain modalities, zeolites promoted by metal and not promoted have the same SAR. In other modalities, zeolites promoted by metal and not promoted have different SARs. In certain modalities, non-promoted zeolite has a higher SAR compared to metal-promoted zeolite. For example, metal-promoted zeolite can have a SAR of about 10 to about 14 and non-promoted zeolite can have a SAR of about 15 to about 25; or the metal promoted zeolite can have a SAR of about 15 to about 22 and the non-promoted zeolite can have a SAR of about 22 to about 30.
    [0023] Zeolites useful in the present invention have a structure selected from the group consisting of CHA, AEI, AFX, LEV, and SFW. Any aluminosilicate isotype of these structures is suitable for the present invention. In certain embodiments, zeolite is a substantially pure phase of a single structure. In other embodiments, the primary crystalline phase of zeolite is one of the structures mentioned above, but it also includes other crystalline phases. A substantially pure zeolite phase contains at least 95 weight percent of a structure. Mixed phase zeolites can contain 75 to 95 weight percent of one structure and 5 to 25 weight percent of a second structure. Examples of the combined phases include AEI and FAU or AEI and CHA. In certain embodiments, zeolite is an AEI / CHA intergrowth.
    [0024] Scanning electron microscope can determine the morphology and size of the zeolite crystallite according to the invention. It is desirable that the average particle size and / or average crystal size of the aluminosilicate zeolite as measured by SEM is greater than about 0.50 μm, such as having a size range with a lower limit of about 1 μm , about 2 μm, about 3 μm, or about 5 μm; and an upper limit of about 8 μm, about 10 μm, or about 15 μm. In certain embodiments, the particle size d50 and / or d90 or the particle size of the zeolite is within one of the size ranges mentioned above. In certain embodiments, the zeolite crystals and / or agglomerations are ground to be within one of these ranges. In certain embodiments, the crystal size and / or particle size of the metal promoted zeolite is the same as the crystal and / or particle size of the non-promoted zeolite. In other embodiments, the crystal and / or particle size of the zeolite promoted by metal is larger than the crystal and / or particle size of the non-promoted zeolite. In other embodiments, the crystal and / or particle size of the zeolite promoted by metal is smaller than the crystal and / or particle size of the non-promoted zeolite.
    [0025] Most of the zeolite aluminosilicate structure is constructed of alumina and silica, but metal-promoted zeolite may include different metal structures than aluminum (ie, metal-substituted zeolites). As used herein, the term "substituted by metal" in connection with a zeolite means a zeolite structure having one or more aluminum or silicon structure atoms replaced by atoms replaced by a replacement metal. In contrast, the term "metal exchange" means a zeolite having extra structure or free metal ions associated with the frame structure, but they are not part of the structure itself. Examples of metal-substituted structures include those that comprise copper-structure atoms. Preferably, non-promoted zeolites.
    [0026] Preferably, the non-promoted zeolite component is H +, NH4 +, alkali metal, alkaline earth metal form, or some combinations of one or more metals to incorporate aluminum. In particularly preferred embodiments, the non-promoted zeolite is in an H + form, an NH4 + form, or a combination thereof. In certain embodiments, the non-promoted zeolite, and / or the metal-promoted zeolite, is substantially free of alkali metals, alkaline earth metals, or both alkali metals and alkaline earth metals. As used here, the term "substantially free" with respect to an alkali metal or alkaline earth metal means that the zeolite does not have a noticeable amount of the particular metal. That is, the particular metal is not present in an amount that can affect the basic physical and / or chemical properties of zeolite, particularly with respect to the ability of zeolite to selectively reduce or store NOx. For example, a zeolite material substantially free of a alkali metal or alkaline earth metal contains less than 3 weight percent, more preferably less than 1 weight percent, and even more preferably less than 0.1 weight percent of that metal.
    [0027] In certain embodiments, the metal-promoted zeolite component and / or the non-promoted zeolite component contains at least one of potassium, magnesium, and calcium disposed on the surface of the zeolite and / or within the pores of the zeolite, with calcium being particularly preferred. In certain embodiments, the catalyst is essentially free of any alkali metal or alkaline earth metal except calcium and potassium. In certain embodiments, the metal-promoted zeolite component and / or the non-promoted zeolite component is essentially free of any alkali metal or alkaline earth metal except calcium. And in certain other embodiments, the metal-promoted zeolite component and / or the non-promoted zeolite component is essentially free of any alkali metal or alkaline earth metal except potassium. In certain preferred embodiments, the metal-promoted zeolite component is essentially free of alkali metal and alkaline earth metal and the non-promoted zeolite component contains calcium, but otherwise it is essentially free of alkali metal and alkaline earth metal.
    [0028] In certain embodiments, the non-promoted zeolite contains at least about 0.1 weight percent calcium relative to the weight of the non-promoted zeolite, such as about 0.1 to about 3 weight percent, about 0 , 1 to about 1 weight percent, or about 1 to about 3 weight percent.
    [0029] In certain embodiments, alkali metal and / or alkaline earth metal (collectively AM) is present in the zeolite material promoted by metal in an amount with respect to the amount of promoter metal (M) in the zeolite. Preferably, M and AM are present, respectively, in a molar ratio of about 15: 1 to about 1: 1, for example about 10: 1 to about 2: 1, about 10: 1 to about 3 : 1, or about 6: 1 to about 4: 1, particularly where M is copper and AM is calcium. In certain embodiments where the zeolite promoted by metal includes calcium, the amount of copper present is less than about 3 percent by weight, such as less than about 2.5 percent by weight, less than about 2 percent by weight, or less than about 1 percent by weight, based on the weight of the zeolite.
    [0030] In certain embodiments, the relative cumulative amount of promoter metal (M) and alkali metal and / or alkaline earth metal (AM) is present in a zeolite material in an amount with respect to the amount of aluminum in the zeolite, namely the structure aluminum. As used here, the ratio (M + AM): Al is based on the relative molar quantities of M + AM for molar structure Al in the corresponding zeolite. In certain embodiments, the catalyst material has a ratio (M + AM): Al of not more than about 0.6. In certain embodiments, the ratio (M + AM): Al is not more than 0.5, for example about 0.05 to about 0.5, about 0.1 to about 0.4, or about from 0.1 to about 0.2.
    [0031] The promoter metal and alkali metal / alkaline earth metal can be added to the molecular sieve through any known technique such as ion exchange, impregnation, isomorphic substitution, etc. The promoting metal and the alkali metal or alkaline earth metal can be added to a zeolite material in any order (for example, the metal can be exchanged before, after, or concurrently with the alkali metal or alkaline earth metal), but preferably the alkali metal or alkaline earth metal is added before or concurrently with the promoter metal, particularly when the alkaline earth metal is calcium and the promoter metal is copper.
    [0032] In certain embodiments, the metal-promoted zeolite component and / or the non-promoted zeolite component contain a relatively large amount of cerium (Ce). In certain embodiments, the cerium concentration in the catalyst material is present in a concentration of at least about 1 percent by weight, based on the total weight of the zeolite promoted by metal and / or not promoted. Examples of preferred concentrations include at least about 2.5 weight percent, at least about 5 weight percent, at least about 8 weight percent, at least about 10 weight percent, about 1.35 percent to about about 13.5 weight percent, about 2.7 to about 13.5 weight percent, about 2.7 to about 8.1 weight percent, about 2 to about 4 weight percent, about from 2 to about 9.5 weight percent, and from 5 to about 9.5 weight percent, based on the total weight of the zeolite.
    [0033] In certain modalities, the Ce concentration exceeds the maximum theoretical amount available for exchange in zeolite promoted by metal. Appropriately, in some embodiments, Ce is present in more than one form, such as Ce ions, monomeric ceria, oligomeric ceria, and combinations thereof, provided that said oligomeric ceria has an average crystal size less than 5 μm, for example less than 1 μm, about 10 nm to about 1 μm, about 100 nm to about 1 μm, about 500 nm to about 1 μm, about 10 to about 500 nm, about 100 to about 500 nm, and about 10 to about 100 nm. As used here, the term "monomeric ceria" means CeO2 as individual molecules or portions that reside freely in and / or the zeolite or weakly linked to the zeolite. As used here, the term "oligomeric ceria" means monocrystalline CeO2 that resides freely in and / or within the zeolite or weakly linked with the zeolite.
    [0034] Catalysts of the present invention are applicable to heterogeneous catalytic reaction systems (i.e., solid catalyst in contact with a gaseous reagent). To improve the contact surface area, mechanical stability, and / or fluid flow characteristics, catalysts can be arranged in and / or within a substrate, preferably a porous substrate. In certain embodiments, a washable coating containing the catalyst is applied to an inert substrate, such as corrugated metal plate or an alveolar cordierite brick. Alternatively, the catalyst is kneaded together with other components such as fillers, binders, and reinforcing agents, in an extrusable paste that is then extruded through a matrix to form a honeycomb brick. Suitably, in certain embodiments, a catalyst article is provided comprising a catalyst mixture as described herein coated in and / or incorporated into a substrate.
    [0035] Certain aspects of the invention provide a washable catalytic coating. The washable coating comprising the catalyst mixture described herein is preferably a solution, suspension, or slurry. Suitable coatings include surface coatings, coatings that penetrate a portion of the substrate, coatings that permeate the substrate, or some combination thereof. A washable coating can also include non-catalytic components, such as fillers, binders, stabilizers, rheology modifiers, and other additives, including one or more of alumina, silica, silica, non-zeolite alumina, titania, zirconia, ceria. In certain embodiments, the catalyst composition may comprise pore forming agents such as graphite, cellulose, starch, polyacrylate, and polyethylene, and the like. These additional components do not necessarily catalyze the desired reaction, but instead improve the effectiveness of catalytic material, for example, increasing its operating temperature range, increasing the catalyst's contact surface area, increasing the catalyst's adhesion to a substrate, etc.
    [0036] Two of the most common substrate designs are plate and honeycomb. Preferred substrates, particularly for mobile applications, include flow monoliths having a so-called honeycomb geometry that comprise multiple adjacent parallel channels that are open at both ends and generally extend from the entrance face to the exit face of the substrate and result in a high surface area to volume ratio. For certain applications, the honeycomb flow monolith preferably has a high cell density, for example, about 600 to 800 cells per square inch, and / or an average internal wall thickness of about 0.18 to 0.35 mm, preferably about 0.20 to 0.25 mm. For certain other applications, the honeycomb flow monolith preferably has a low cell density of about 150 to 600 cells per square inch, more preferably about 200 to 400 cells per square inch. Preferably, the alveolar monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramics, and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, α-alumina, mullite, for example, mullite acicular, pollucite, a thermet such as Al2OsZFe, Al2O3 / Ni or B4CZFe, or composites comprising segments of any two or more of them. Preferred materials include cordierite, silicon carbide, and alumina titanate.
    [0037] Plate type catalysts have lower pressure drops and are less susceptible to clogging and fouling than honeycomb types, which is advantageous in high efficiency stationary applications, but plate configurations can be much larger and more expensive. A honeycomb configuration is typically smaller than a plate type, which is an advantage in many applications in mobile applications, but has greater pressure drops and clogging more easily. In certain embodiments, the plate substrate is constructed of metal, preferably corrugated metal.
    [0038] In certain embodiments, the invention is a catalyst article made by a process described here. In a particular embodiment, the catalyst article is produced by a process that includes the steps of applying the catalyst mixture, preferably as a washable coating, to a substrate as a layer both before and after at least one additional layer of another composition for treating exhaust gas was applied to the substrate.
    [0039] In certain embodiments, the catalyst mixture is incorporated into a catalytic article or an exhaust gas treatment system in which the catalyst mixture is arranged on a substrate as a layer or zone and another composition, such as a catalyst of oxidation, reduction catalyst, trapping component, or NOx storage component, is arranged on the same substrate or a different substrate as another layer or zone. The layers or zones can be arranged on the same or different substrates and can overlap, be adjacent, and / or be consecutive. The catalyst mixture can be arranged as an overlay layer or an upstream zone with respect to the second catalyst. Alternatively, the catalyst mixture can be arranged as an underlying layer or a zone downstream with respect to the second catalyst. In certain embodiments, the second catalyst layer or zone contains one or more noble metals, such as gold, silver, and platinum group metals, such as platinum, palladium, rhodium, ruthenium, or rhenium, supported on a metal oxide refractory such as alumina, ceria, titania, silica, or some combination thereof. In certain embodiments, the second layer of catalyst or zone contains a zeolite promoted by metal. In certain embodiments, particularly exhaust gas treatment systems that use a second catalyst, the catalyst mixture described here is used as an N2O reduction catalyst.
    [0040] To reduce the amount of space required for an exhaust system, individual exhaust components in certain modalities are designed to perform more than one function. For example, applying an SCR catalyst to a wall flow filter substrate instead of a flow through substrate serves to reduce the overall size serves to reduce the overall size of an exhaust treatment system by allowing a substrate to serve the purpose. two functions, namely catalytically reducing the NOx concentration in the exhaust gas and mechanically removing soot from the exhaust gas. Appropriately, in certain embodiments, the substrate is an alveolar wall flow filter or partial filter. Wall flow filters are similar to the cellular flow substrates in that they contain a plurality of adjacent parallel channels. However, the flow-through alveolar substrate channels are open at both ends, where the wall flow substrate channels have a linked end, where the bonding occurs at opposite ends of adjacent channels in an alternating pattern. The connection of alternating channel ends prevents gas entering the substrate inlet side of the straight flow through the channel and exiting. Instead, the exhaust gas enters the front of the substrate and travels to about half of the channels where it is forced through the channel walls before entering the second half of the channels and exiting the rear face of the substrate.
    [0041] The substrate wall has a porosity and pore size that is permeable to gas, but traps a large portion of particulate material, such as soot, from gas when gas passes through the wall. Preferred wall flow substrates are highly efficient filters. Wall flow filters for use with the present invention preferably have an efficiency of at least 70%, at least about 75%, at least about 80%, or at least about 90%. In certain embodiments, the efficiency will be from about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. Here, efficiency is relative to soot and other particles sized in a similar way and for particular concentrations typically found in conventional diesel exhaust gas. For example, particulates in diesel exhaust can vary in size from 0.05 microns to 2.5 microns. Thus, efficiency can be based on this range or sub-range, such as 0.1 to 0.25 micron, 0.25 to 1.25 micron, or 1.25 to 2.5 micron.
    [0042] Porosity is a measure of the percentage of empty space in a porous substrate and is related to the back pressure in an exhaust system: in general, the lower the porosity, the higher the back pressure. Preferably, the porous substrate has a porosity of about 30 to about 80%, for example about 40 to about 75%, about 40 to about 65%, or from about 50 to about 60% .
    [0043] The pore interconnectivity, measured as a percentage of the total void volume of substrate, is the degree to which pores, void, and / or channels are joined to form continuous paths through a porous substrate, that is, the from the input face to the exit face. In contrast to the pore interconnectivity is the sum of the closed pore volume and the volume of the pores that have a conduit for only one of the substrate surfaces. Preferably, the porous substrate has a volume of pore interconnectivity of at least about 30%, more preferably at least about 40%.
    [0044] The average pore size of the porous substrate is also important for filtration. The average pore size can be determined by any acceptable means, including mercury porosimetry. The average pore size of the porous substrate should be high enough to promote low back pressure, while providing adequate efficiency both by the substrate alone, by promoting a layer of soot cake on the substrate surface, or combination of both. Preferred porous substrates have an average pore size of about 10 to about 40 μm, for example about 20 to about 30 μm, about 10 to about 25 μm, about 10 to about 20 μm, about 20 to about 25 μm, about 10 to about 15 μm, and about 15 to about 20 μm.
    [0045] In general, the production of an extruded solid body containing the catalyst mixture involves mixing the metal-promoted zeolite and the non-promoted zeolites, a binder, an optional organic viscosity enhancing compound into a homogeneous paste that is then added to a binder / matrix component or a precursor thereof and optionally one or more of stabilized ceria and inorganic fibers. The mixture is compacted in a mixing or kneading device or an extruder. The mixtures also contain additives such as pore builders, plasticizers, surfactants, lubricants, dispersants to promote physical characteristics in the extruded structure or as processing aids to improve humidification and therefore produce a uniform batch. The resulting plastic material is then molded, in particular using an extrusion press or an extruder including an extrusion die, and the resulting moldings are dried and calcined. Organic additives are "burned" during calcination of the extruded solid body. Preferably, the catalyst mixture is dispersed therethrough, and preferably equally throughout, the entire catalyst body.
    [0046] The catalyst mixture can also be applied with a washable coating or otherwise applied as the extruded solid body as one or more sublayers that reside on the surface or penetrate completely or partially into the extruded solid body.
    [0047] The catalyst mixtures described here can promote the reaction of a reducer, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O). Thus, in one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides with a reducer (that is, an SCR catalyst). Examples of such reducers include hydrocarbons (for example, C3 to C6 hydrocarbons) and nitrogen reducers such as ammonia and hydrazine ammonia or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, carbonate ammonium hydrogen or ammonium formate.
    [0048] The catalyst mixtures described here can also reduce ammonia leakage. Thus, in another embodiment, the catalyst can be formulated to favor the storage of NH3 to reduce secondary NOx produced by oxidation of ammonia with oxygen, particularly an ammonia concentration typically found downstream of an SCR catalyst. In certain embodiments, the catalyst mixture containing metal promoted and non-promoted zeolite is arranged as a top layer by an oxidative underlying layer, wherein the underlying layer comprises a platinum group metal catalyst (PGM) or a non-PGM catalyst . Preferably, the catalyst component in the underlying layer is arranged on a high surface area support, including but not limited to alumina.
    [0049] Appropriately, a method is provided for reducing NOx compounds and / or controlling NH3 leakage in an exhaust gas, which comprises contacting the gas with a catalyst composition described here for the catalytic reduction of compounds of NOx for a sufficient time to reduce the level of NOx and / or NH3 compounds in the gas. In certain embodiments, a catalyst article is provided having an ammonia leak catalyst disposed downstream of the Selective Catalytic Reduction (SCR) catalyst. In such embodiments, the ammonia leak catalyst oxidizes at least a portion of any nitrogen reducer that is not consumed by the Selective Catalytic Reduction process. For example, in certain embodiments, the ammonia leak catalyst is disposed on the outlet side of a wall flow filter and an SCR catalyst is disposed on the upstream side of a filter. In certain other embodiments, the ammonia leak catalyst is disposed at the downstream end of a flow-through substrate and an SCR catalyst is disposed at the upstream end of the flow-through substrate. In other embodiments, the ammonia leak catalyst and SCR catalyst are arranged on separate bricks within the exhaust system. These separate bricks can be adjacent to, and be in contact with, each other or separated by a specific distance, provided that they are in fluid communication with each other and provided that the SCR catalyst brick is disposed upstream of the escape catalyst brick of ammonia.
    [0050] In certain modalities, the SCR and / or ASC process is carried out at a temperature of at least 150 ° C. In another embodiment, the processes take place at a temperature from about 150 ° C to about 750 ° C. In a particular embodiment, the temperature range is from about 175 to about 550 ° C. In another mode, the temperature range is 175 to 400 ° C. In yet another embodiment, the temperature range is 450 to 900 ° C, preferably 500 to 750 ° C, 500 to 650 ° C, 450 to 550 ° C, or 650 to 850 ° C. Modalities using temperatures greater than 450 ° C are particularly useful for treating exhaust gases from a light and heavy-duty diesel engine that is equipped with an exhaust system comprising (optionally catalyzed) diesel particulate filters that are regenerated in an active or passive manner, in which the catalyst mixture described here is arranged on the outlet side of the filter.
    [0051] According to another aspect of the invention, a method is provided for treating an exhaust gas, preferably for the reduction of NOX compounds and / or NH3 leakage in the gas, which comprises one or more of the following steps: (a ) accumulate and / or burn soot that is in contact with the entrance of a catalytic filter; (b) introducing a nitrogen reducing agent into the exhaust gas stream before contacting the catalytic filter, preferably without an intervening catalytic step involving the NOx treatment and the reducer; (c) generating NH3 by a NOx-absorbing catalyst or poor NOx trapping, and preferably using such NH3 as a reducer in a downstream SCR reaction; (d) contacting the exhaust gas stream with DOC to oxidize hydrocarbon based on the soluble organic fraction (SOF) and / or carbon monoxide to CO2, and / or oxidize NO to NO2, which in turn can be used to oxidize particulate matter in a particulate filter; and / or reduce the particulate material (PM) in the exhaust gas; (e) contacting the exhaust gas with one or more flow SCR catalyst devices through the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting the exhaust gas with an ammonia leak catalyst, preferably downstream of the SCR catalyst to oxidize most, if not all, of the ammonia before emitting the exhaust gas to the atmosphere or passing the gas exhaust through a recirculation cycle before the exhaust gas enters / re-enters the engine.
    [0052] In another embodiment, all or at least a portion of the nitrogen-based reducer, particularly NH3, for consumption in the SCR process can be supplied by a NOx adsorbent catalyst (NAC), a poor NOx trap ( LNT), or a NOx reduction storage / catalyst (NSRC), arranged upstream of the SCR catalyst, for example, the SCR catalyst of the present invention arranged in a wall flow filter. NAC components useful in the present invention include a catalyst combination of a base material (such as alkali metal, alkaline earth metal or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof), and a precious metal (such as platinum), and optionally a reducing catalyst component, such as rhodium. Specific types of basic material useful in NAC include cesium oxide, potassium oxide, magnesium oxide, sodium oxide, calcium oxide, strontium oxide, barium oxide, and combinations thereof. The precious metal is preferably present at about 357.1 (10) to about 7,142 g / m3 (200 g / ft3), such as 714.2 (20) to 2,142.6 g / m3 (60 g / ft3) . Alternatively, the precious metal of the catalyst is characterized by the average concentration which can be from about 1,428.4 (40) to about 3.571 g / m3 (100 grams / ft3).
    [0053] Under certain conditions, during periodically rich regeneration events, NH3 can be generated by a NOx adsorbing catalyst. The SCR catalyst downstream of the NOx adsorbing catalyst can improve the overall system's NOx reduction efficiency. In the combined system, the SCR catalyst is able to store the NH3 released from the NAC catalyst during rich regeneration events and uses the stored NH3 to selectively reduce some or all of the NOx that escapes through the NAC catalyst during the conditions of normal poor operation.
    [0054] The method for treating exhaust gas as described here can be carried out on an exhaust gas derived from a combustion process, such as from an internal combustion engine (either mobile or stationary), a turbine gas and power plants burning oil or coal. The method can also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, ovens, the chemical processing industry, cooking ovens, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used to treat exhaust gas from a low-burning internal combustion engine, such as a matrix engine, a low-burning gasoline engine or an engine powered by liquid petroleum gas or natural gas.
    [0055] In certain aspects, the invention is a system for treating exhaust gas generated by the combustion process, such as from an internal combustion engine (either mobile or stationary), a gas turbine, flare energy plants coal and oil, and the like. Such systems include a catalytic article comprising the catalyst mixture described herein and at least one additional component to treat the exhaust gas, wherein the catalytic article and at least one additional component are designed to function as a coherent unit.
    [0056] In certain embodiments, the system comprises a catalytic article comprising a mixture of catalyst described here, a conduit for directing an exhaust gas flow, a source of nitrogen reducer disposed upstream of the catalytic article. The system may include a controller for the measurement of the nitrogen reducer for exhaust gas flowing only when it is determined that the zeolite catalyst is capable of catalyzing the NOx reduction at or above a desired efficiency, such as above 100 ° C, above 150 ° C or above 175 ° C. The measurement of the nitrogen reducer can be arranged such that 60% to 200% of theoretical ammonia is present in the exhaust gas that enters the SCR catalyst calculated in 1: 1 NH3 / NO and 4: 3 NH3 / NO2.
    [0057] In another embodiment, the system comprises an oxidation catalyst (for example, a diesel oxidation catalyst (DOC)) to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a measurement of the nitrogen reducer for the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a gas stream that enters the SCR zeolite catalyst having a NO to NO2 ratio of from about 4: 1 to about 1: 3 by volume, for example. example in an exhaust gas temperature at the oxidation catalyst inlet from 250 ° C to 450 ° C. The oxidation catalyst may include at least one metal of the platinum group (or some combination thereof), such as platinum, palladium, or rhodium, coated on a flow-through monolith substrate. In one embodiment, the at least one metal in the platinum group is platinum, palladium or a combination of platinum and palladium. The platinum group metal can be supported in a washable coating component with a high surface area such as alumina, a zeolite such as an aluminosilicate zeolite, silica, silica, non-zeolite alumina, ceria, zirconia, titania or a mixed or compound oxide containing both ceria and zirconia.
    [0058] In an additional embodiment, a suitable filter substrate is located between the oxidation catalyst and the SCR catalyst. Filter substrates can be selected from any of those mentioned above, for example, wall flow filters. Where the filter is catalyzed, for example with an oxidation catalyst of the type discussed above, preferably the nitrogen reducer measuring point is located between the filter and a zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for measuring the nitrogen reducer can be located between the oxidation catalyst and the filter. EXAMPLES Example 1 - NOx conversion performance of the catalyst mixture.
    [0059] A sample of a zeolite form of NH4 +, having a CHA structure, and having a SAR of about 25 was added to a solution of copper acetate at room temperature to produce a copper exchange zeolite. The copper exchange zeolite has been dried and calcined at 600 ° C and results in a zeolite having about 3.3 weight percent copper based on the weight of the zeolite.
    [0060] Samples of catalyst mixtures were prepared by mixing a portion of the zeolite material promoted with copper described above with a portion of the same zeolite, but without the exchanged copper. Eight such samples were prepared in which the proportion of zeolite promoted by copper in the mixture varies from about 10 weight percent to about 50 weight percent.
    [0061] The exchange zeolite with copper and the mixture of catalysts were thermally aged at 900 ° C for 3 hours.
    [0062] The NOx conversion performance of each of these samples were tested under conditions similar to 200 ° C and 500 ° C. The data for these tests are plotted in Figures 1 and 2.
    [0063] The test results show that the addition of pure zeolite to a copper exchange zeolite increased the NOx conversion performance of the aged catalyst material over a wide temperature range. Example 2 - NOx conversion performance of catalyst mixtures
    [0064] A sample of a zeolite form of NH4 +, having a CHA structure, and having a SAR of about 13 was added to a copper acetate solution at room temperature to produce a copper exchange zeolite. The copper exchange zeolite was dried and calcined at about 600 ° C and resulted in a zeolite having about 3.5 weight percent copper based on the weight of the zeolite.
    [0065] A portion of this sample was mixed with a form of NH4 + zeolite, having a CHA structure, and having a SAR of about 22, to produce a mixture containing about 35 weight percent of the copper exchange zeolite and about 65 percent by weight of pure zeolite.
    [0066] The conversion performance of fresh NOx (ie, not aged) from copper exchange zeolite and the mixture was tested at 600 ° C. The NOx conversion performance of copper exchange zeolite and the mixture after hydrothermal aging at 900 ° C for 1 hour was also tested at 600 ° C. The data for these tests are shown in Figure 3.
    [0067] The test results show that the addition of pure zeolite to the copper exchange zeolite increased the high temperature NOx conversion performance of the catalyst material.
    权利要求:
    Claims (12)
    [0001]
    1. Catalyst for the treatment of an exhaust gas, characterized by the fact that it comprises a mixture of: (a) a first zeolite exchanged with transition copper; and (b) a second non-promoted zeolite that is free of a solution of transition metals exchanged in at least one of the H + form, NH4 + form, alkali metal form, or alkaline earth metal form, in which the first promoted copper zeolite and the second non-promoted zeolites have the same main chain structure and the main chain structure is selected from CHA, AEI, AFX, LEV and SFW.
    [0002]
    2. Catalyst according to claim 1, characterized by the fact that the second zeolite contains calcium.
    [0003]
    3. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper and the second non-promoted zeolite have different proportions of silica-to-alumina.
    [0004]
    4. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper has a lower proportion of silica-to-alumina compared to the second non-promoted zeolite.
    [0005]
    5. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper and the second non-promoted zeolite have, independently, a silica-to-alumina ratio of 10 to 35.
    [0006]
    6. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper and the second non-promoted zeolite have the same proportion of silica-to-alumina.
    [0007]
    7. Catalyst according to claim 1, characterized by the fact that the second non-promoted zeolite and the first zeolite exchanged with copper are present in a relative proportion of 0.1 to 1.
    [0008]
    8. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper and the second non-promoted zeolite have a CHA main chain.
    [0009]
    9. Catalyst according to claim 1, characterized by the fact that the first zeolite exchanged with copper and the second non-promoted zeolite have an AEI main chain.
    [0010]
    10. Catalyst article for exhaust gas treatment, characterized by the fact that it comprises a porous alveolar substrate containing a catalyst as defined in claim 1.
    [0011]
    11. Method for treating exhaust gas, characterized by the fact that it comprises contacting an exhaust gas stream containing NOX with a reducer in the presence of a catalyst as defined in claim 1; where contact selectively reduces at least a portion of NOX to N2 and water.
    [0012]
    12. Method according to claim 11, characterized by the fact that the contact occurs at a temperature of 150 to 600 ° C.
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    同族专利:
    公开号 | 公开日
    WO2015028805A1|2015-03-05|
    KR102227793B1|2021-03-15|
    GB201519589D0|2015-12-23|
    JP2019104011A|2019-06-27|
    JP2016536126A|2016-11-24|
    EP3038749A1|2016-07-06|
    GB2534644A|2016-08-03|
    DE102014112413A1|2015-03-05|
    CN105611998A|2016-05-25|
    US9278343B2|2016-03-08|
    RU2016111605A|2017-10-05|
    CN110394188A|2019-11-01|
    KR20160048192A|2016-05-03|
    GB2519648A|2015-04-29|
    CN105611998B|2019-11-08|
    GB201415287D0|2014-10-15|
    RU2016111605A3|2018-03-06|
    JP6559673B2|2019-08-14|
    JP6875428B2|2021-05-26|
    RU2669556C2|2018-10-12|
    GB2534644B|2019-04-17|
    US20150064088A1|2015-03-05|
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    法律状态:
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